Process for producing polymers

ABSTRACT

A process of using a catalyst composition to polymerize at least one monomer to produce a polymer. The process comprises contacting the catalyst composition and at least one monomer in a polymerization zone under polymerization conditions to produce the polymer. The catalyst composition is produced by a process comprising contacting at least one organometal compound, at least one treated solid oxide compound, and at least one organoaluminum compound.

This application is a divisional of application Ser. No. 09/080,619filed May 18, 1998, now U.S. Pat. No. 6,300,271.

FIELD OF THE INVENTION

This invention is related to the field of compositions that can be usedto polymerize monomers into at least one polymer.

BACKGROUND OF THE INVENTION

The production of polymers is a multi-billion dollar business. Thisbusiness produces billions of pounds of polymers each year. Millions ofdollars have been spent on developing technologies that can add value tothis business.

One of these technologies is called metallocene catalyst technology.Metallocene catalysts have been known since about 1960, however, theirlow productivity did not allow them to be commercialized. About 1975, itwas discovered that contacting one part water with two partstrimethylaluminum to form methyl aluminoxane, and then contacting suchmethyl aluminoxane with a metallocene compound, formed a metallocenecatalyst that had greater activity. However, it was soon realized thatlarge amounts of expensive methyl aluminoxane were needed to form anactive metallocene catalyst. This has been a significant impediment tothe commercialization of metallocene catalysts.

Borate compounds have been use in place of large amounts of methylaluminoxane. However, this is not satisfactory, since borate compoundsare very sensitive to poisons and decomposition, and can also be veryexpensive.

It should also be noted that having a heterogeneous catalyst isimportant. This is because heterogeneous catalysts are required for mostmodern commercial polymerization processes. Furthermore, heterogeneouscatalysts can lead to the formation of substantially uniform polymerparticles that have a high bulk density. These types of substantiallyuniformed particles are desirable because they improve the efficiency ofpolymer production and transportation. Efforts have been made to produceheterogeneous metallocene catalysts, however, these catalysts have notbeen entirely satisfactory.

Therefore, the inventors provide this invention to solve these problems.

SUMMARY OF THE INVENTION

An object of this invention is to provide a process that produces acomposition that can be used to polymerize monomers into at least onepolymer.

Another object of this invention is to provide said composition.

Another object of this invention is to provide a process to polymerizemonomers into at least one polymer using said composition.

Another object of this invention is to provide a manufacture thatcomprises at least one said polymer.

Another object of this invention is to provide a machine that comprisesat least one said manufacture.

In accordance with one embodiment of this invention, a process toproduce a composition of matter is provided. Said process comprises (oroptionally, consists essentially of, or consists of) contacting anorganometal compound, a treated solid oxide compound, and anorganoaluminum compound to produce said composition, wherein saidcomposition consists essentially of (or optionally, consists of) apost-contacted organometal compound, a post-contacted treated solidoxide compound, and optionally, a post-contacted organoaluminumcompound.

In accordance with another embodiment of this invention, a compositionof matter is provided. Said composition consists essentially of apost-contacted organometal compound, a post-contacted treated solidoxide compound, and optionally, a post-contacted organoaluminumcompound.

In accordance with another embodiment of this invention, a process topolymerize monomers into at least one polymer using said composition isprovided. Said process comprises contacting said composition withmonomers.

In accordance with another embodiment of this invention a manufacture isprovided. Said manufacture comprises at least one said polymer.

In accordance with another embodiment of this invention a machine isprovided. Said machine comprises at least two said manufactures.

These objects, and other objects, will become more apparent to thosewith ordinary skill in the art after reading this disclosure.

It should be noted that the phrase “consisting essentially of” meansthat the only other items (such as, for example, process steps, andother compounds) included within the scope of the claims are those itemsthat do not materially affect the basic and novel characteristics of theclaimed invention.

It should also be noted that the phrase “consisting of” means that theno other items (such as, for example, process steps, and othercompounds) are included within the scope of the claims, except itemsthat are impurities ordinarily associated with a composition, or itemsthat are process steps ordinarily associated with a process.

DETAILED DESCRIPTION OF THE INVENTION

Organometal compounds used in this invention have the following generalformula.

(X¹)(X²)(X³)(X⁴)M¹  FORMULA ONE

In this formula, M¹ is selected from the group consisting of titanium,zirconium, and hafnium. Currently, it is most preferred when M¹ iszirconium.

In this formula (X¹) is independently selected from the group consistingof (hereafter “Group OMC-I”) cyclopentadienyls, indenyls, fluorenyls,substituted cyclopentadienyls, substituted indenyls, such as, forexample, tetrahydroindenyls, and substituted fluorenyls, such as, forexample, octahydrofluorenyls.

The substituents on thy substituted cyclopentadienyls, substitutedindenyls, and substituted fluorenyls, can be aliphatic groups, cyclicgroups, combinations of aliphatic and cyclic groups, and organometallicgroups, as long as these groups do not substantially, and adversely,affect the polymerization activity of the composition. Additionally,hydrogen can be a substituent.

Suitable examples of aliphatic groups are hydrocarbyls, such as, forexample, paraffins and olefins. Suitable examples of cyclic groups arecycloparaffins, cycloolefins, cycloacetylenes, and arenes. Additionally,alkylsilyl groups where each alkyl contains 1-12 carbon atoms, alkylhalide groups where each alkyl contains 1-12 carbon atoms, or halides,can also be used.

Suitable examples of such substituents are methyl, ethyl, propyl, butyl,tert-butyl, isobutyl, amyl, isoamyl, hexyl, cyclohexyl, heptyl, octyl,nonyl, decyl, dodecyl, 2-ethylhexyl, pentenyl, butenyl, phenyl, chloro,bromo, and iodo.

In this formula (X³) and (X⁴) are independently selected from the groupconsisting of (hereafter “Group OMC-II”) halides, aliphatic groups,cyclic groups, combinations of aliphatic and cyclic groups, andorganometallic groups, as long as these groups do not substantially, andadversely, affect the polymerization activity of the composition.

Suitable examples of aliphatic groups are hydrocarbyls, such as, forexample, paraffins and olefins. Suitable examples of cyclic groups arecycloparaffins, cycloolefins, cycloacetylenes, and arenes. Currently, itis preferred when (X³) and (X⁴) are selected from the group consistingof halides and hydrocarbyls, where such hydrocarbyls have from 1 to 10carbon atoms. However, it is most preferred when (X³) and (X⁴) areselected from the group consisting of fluoro, chloro, and methyl.

In this formula, (X²) can be selected from either Group OMC-I or GroupOMC-II.

When (X²) is selected from Group OMC-I, it should be noted that (X¹) and(X²) can be joined with a bridging group, such as, for example,aliphatic bridging groups, cyclic bridging groups, combinations ofaliphatic and cyclic bridging groups, and organometallic bridginggroups, as long as the bridging group does not substantially, andadversely, affect the polymerization activity of the composition.

Suitable examples of aliphatic bridging groups are hydrocarbyls, suchas, for example, paraffins and olefins. Suitable examples of cyclicbridging groups are cycloparaffins, cycloolefins, cycloacetylenes, andarenes. Additionally, it should be noted that silicon and germanium arealso good bridging units.

Various processes are known to make these compositions. See, forexample, U.S. Pat. Nos. 4,939,217; 5,210,352; 5,436,305; 5,401,817;5,631,335, 5,571,880; 5,191,132; 5,480,848; 5,399,636; 5,565,592;5,347,026; 5,594,078; 5,498,581; 5,496,781; 5,563,284; 5,554,795;5,420,320; 5,451,649; 5,541,272; 5,705,478; 5,631,203; 5,654,454;5,705,579; and 5,668,230; the entire disclosures of which are herebyincorporated by reference.

Specific examples of such compositions are as follows:

bis(cyclopentadienyl) hafnium dichloride;

bis(cyclopentadienyl) zirconium dichloride;

[ethyl(indenyl)₂] hafnium dichloride;

[ethyl(indenyl)₂] zirconium dichloride;

[ethyl(tetrahydroindenyl)₂] hafnium dichloride;

[ethyl(tetrahydroindenyl)₂] zirconium dichloride;

bis(n-butylcyclopentadienyl) hafnium dichloride;

bis(n-butylcyclopentadienyl) zirconium dichloride;

((dimethyl)(diindenyl) silane) zirconium dichloride;

((dimethyl)(diindenyl) silane) hafnium dichloride:

((dimethyl)(ditetrahydroindenyl) silane) zirconium dichloride;

((dimethyl)(di(2-methyl indenyl)) silane) zirconium dichloride; and

bis(fluorenyl) zirconium dichloride.

Organoaluminum compounds have the following general formula.

Al(X⁵)_(n)(X⁶)_(3-n)  FORMULA TWO

In this formula (X⁵) is a hydrocarbyl having from 1-20 carbon atoms.Currently, it is preferred when (X⁵) is an alkyl having from 1 to 10carbon atoms. However, it is most preferred when (X⁵) is selected fromthe group consisting of methyl, ethyl, propyl, butyl, and isobutyl.

In this formula (X⁶) is a halide, hydride, or alkoxide. Currently, it ispreferred when (X⁶) is independently selected from the group consistingof fluoro and chloro. However, it is most preferred when (X⁶) is chloro.

In this formula “n” is a number from 1 to 3 inclusive. However, it ispreferred when “n” is 3.

Examples of such compounds are as follows:

trimethylaluminum;

triethylaluminum;

tripropylaluminum;

diethylaluminum ethoxide;

tributylaluminum;

triisobutylaluminum hydride;

triisobutylaluminum; and

diethylaluminum chloride.

Currently, triethylaluminum is preferred.

The treated solid oxide compounds are compounds that have had theirLewis acidity increased. It is preferred when said treated solid oxidecompound comprises oxygen and at least one element selected from thegroup consisting of groups 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14,and 15 of the periodic table, including lanthanides and actinides (SeeHawley's Condense Chemical Dictionary, 11 th Edition). However, it ispreferred when the element is selected from the group consisting of Al,B, Be, Bi, Cd, Co, Cr, Cu, Fe, Ga, La, Mn, Mo, Ni, Sb, Si, Sn, Sr, Th,Ti, V, W, P, Y, Zn and Zr. It is important that these treated solidoxide compounds have electron withdrawing ability, while not wanting tobe bound by theory, it is believed that a treated solid oxide compoundshould have a higher Lewis acidity compared to the untreated solid oxidecompound. However, it is hard to accurately measure the Lewis acidity ofthese treated, and untreated solid oxide compounds so other methods havebeen used. Currently, comparing the activities of treated, and untreatedsolid oxide compounds under acid catalyzed reactions is preferred.

Treated solid oxide compounds can be produced in a variety of ways, suchas, for example, by gelling, co-gelling, or impregnation of one compoundonto another, followed by calcination.

In general, it is preferred to contact at least one solid oxidecompound, such as, for example, alumina, zirconia, titania, and mixturesthereof or with mixture with other solid oxides such as, for example,silica alumina, with at least one electron-withdrawing anion sourcecompound, to form a first mixture, followed by calcining this firstmixture to form a treated solid oxide compound. In the alternative, asolid oxide compound and an electron-withdrawing anion source compoundcan be contacted and calcined simultaneously. The electron-withdrawinganion source compound is any compound that increases the Lewis acidityof the solid oxide under the conditions given herein for producing thetreated solid oxide compound. These electron-withdrawing anion sourcecompounds increase the Lewis acidity of the solid oxide by contributingto the formation of an electron withdrawing anion, such as, for example,sulfates, halides, and triflate. It should be noted that one or moredifferent electron withdrawing anions can be used.

The acidity of the solid oxide compound can be further enhanced by usingtwo, or more, electron-withdrawing anion source compounds in two, ormore, separate contacting steps. An example of such a process iscontacting at least one solid oxide compound with a firstelectron-withdrawing anion source compound to form a first mixture,followed by calcining this first mixture, followed by contacting with asecond electron-withdrawing anion source compound to form a secondmixture, followed by calcining said second mixture to form a treatedsolid oxide compound. It should be noted that the first and secondelectron-withdrawing anion source compounds can be the same, but arepreferably different.

Suitable examples of solid oxide compounds include, but are not limitedto, Al₂O₃, B₂O₃, BeO, Bi₂O₃, CdO, Co₃O₄, Cr₂O₃, CuO, Fe₂O₃, Ga₂O₃,La₂O₃, Mn₂O₃, MoO₃, NiO, P₂O₅, Sb₂O₅, SiO₂, SnO₂, SrO, ThO₂, TiO₂, V₂O₅,WO₃, Y₂O₃, ZnO, ZrO₂: and mixtures thereof, such as, for example,silica-alumina and silica-zirconia. It should be noted that solid oxidecompounds that comprise Al—O bonds are currently preferred.

It is important that the solid oxide compound is also calcined. Thiscalcining can be conducted in an ambient atmosphere, preferably a dryambient atmosphere, at a temperature in the range of about 200° C. toabout 900° C., and for a time in the range of about 1 minute to about100 hours. Currently, temperatures from about 400° C. to about 800° C.and a time in the range of about 1 hour to about 10 hours, arepreferred.

Treated solid oxide compounds, should have pore volumes greater thanabout 0.01 cc/g, preferably greater than about 0.1 cc/g, and mostpreferably, greater than about 1 cc/g.

Treated solid oxide compounds should have surface areas greater thatabout 1 m₂/g, preferably greater than 100 m²/g, and most preferablygreater than 200 m²/g.

The compositions of this invention can be produced by contacting anorganometal compound, an treated solid oxide compound, and anorganoaluminum compound, together. This contacting can occur in avariety of ways, such as, for example, blending. Furthermore, each ofthese compounds can be fed into the reactor separately, or variouscombinations of these compounds can be contacted together before beingfurther contacted in the reactor, or all three compounds can becontacted together before being introduced into the reactor. Currently,one method is to first contact the organometal compound and the treatedsolid oxide compound together, for about 1 minute to about 24 hours,preferably, about 1 minute to about 1 hour, at a temperature from about10° C. to about 200° C., preferably about 25° C. to about 100° C., toform a first mixture, and then contact this first mixture with anorganoaluminum compound to form the composition. During contacting, orafter contacting, the mixtures or the composition can be calcined. Thiscalcining can be conducted in an ambient atmosphere, preferably a dryambient atmosphere, at a temperature in the range of about 300° C. toabout 900° C., and for a time in the range of about 1 minute to about100 hours. Currently, temperatures from about 500° C. to about 700° C.and a time in the range of about 1 hour to about 10 hours, arepreferred. Currently, it is preferred to use dry nitrogen as the ambientatmosphere.

After contacting, the composition consists essentially of, (or consistsof) a post-contacted organometal compound, a post-contacted treatedsolid oxide compound, and optionally, a post-contacted organoaluminumcompound. It should be noted that the post-contacted treated solid oxidecompound is the majority, by weight, of the composition. Since the exactorder of contacting is not known, it is believed that this terminologybest describes the composition's components.

The composition of this invention has an activity greater than acomposition that uses the same organometal compound, and the sameorganoaluminum compound, but uses untreated Ketjen grade B alumina (seecomparative examples 4, 5, and 6) instead of the treated solid oxidecompounds of this invention. This activity is measured under slurrypolymerization conditions, using isobutane as the diluent, and with apolymerization temperature of 50-150° C., and an ethylene pressure of400-800 psig. The reactor should have substantially no indication of anywall scale, coating or other forms of fouling.

However, it is preferred if the activity is greater than 100 gramspolyethylene per gram of treated solid oxide compound per hour(hereafter “gP/(gS·hr)”), more preferably greater than 250, even morepreferably greater than 500, even more preferably greater than 1000, andmost preferably greater than 2000. This activity is measured underslurry polymerization conditions, using isobutane as the diluent, andwith a polymerization temperature of 90° C., and an ethylene pressure of550 psig. The reactor should have substantially no indication of anywall scale, coating or other forms of fouling.

These compositions are often sensitive to hydrogen and sometimesincorporate comonomers well, and usually produce polymers with a lowHLMI/MI ratio.

One of the important aspects of this invention is that no aluminoxaneneeds to be used in order to form the composition. This also means thatno water is needed to help form such aluminoxanes. This is beneficialbecause water can sometimes kill a polymerization process. Additionally,it should be noted that no borate compounds need to be used in order toform the composition. In summary, this means that the composition, whichis heterogenous, and which can be used for polymerizing monomers, can beeasily and inexpensively produced because of the substantial absence ofany aluminoxane compounds or borate compounds. Additionally, noorganochromium needs to be added, nor any MgCl₂ needs to be added toform the invention.

The monomers useful in this invention, are unsaturated hydrocarbonshaving from 2 to 20 carbon atoms. Currently, it is preferred when themonomer is selected from the group consisting of ethylene, propylene,1-butene, 3-methyl-1-butene, 1-pentene, 3-methyl-1-pentene,4-methyl-1-pentene, 1-hexene, 3-ethyl-1-hexene, 1-heptene, 1-octene,1-nonene, 1-decene, and mixtures thereof. However, when a homopolymer isdesired, it is most preferred to use ethylene, or propylene, as themonomer. Additionally, when a copolymer is desired, it is most preferredto use ethylene and hexene as the monomers.

Processes that can polymerize monomers into polymers are known in theart, such as, for example, slurry polymerization, gas phasepolymerization, and solution polymerization. It is preferred to performa slurry polymerization in a loop reactor. Furthermore, it is even morepreferred to use isobutane as the diluent in a slurry polymerization.Examples of such technology can be found in U.S. Pat. Nos. 4,424,341;4,501,885; 4,613,484; 4,737,280; and 5,597,892; the entire disclosuresof which are hereby incorporated by reference.

It should be noted that under slurry polymerization conditions thesecompositions polymerize ethylene alone, or ethylene with a 1-olefin, orpropylene very well. In particular, the compositions used in thisprocess produce good quality polymer particles without substantiallyfouling the reactor. When the composition is to be used in a loopreactor under slurry polymerization conditions, it is preferred when theparticle size of the solid mixed oxide compound is in the range of about10 to about 1000 microns, preferably 25 to 500 microns, and mostpreferably, about 50 to about 200 microns, for best control duringpolymerization.

After the polymers are produced, they can be formed into variousmanufactures, such as, for example, household containers and utensils,drums, fuel tanks, pipes, geomembranes, and liners. Various processescan form these manufactures. Usually, additives and modifiers are addedto the polymer in order to provide desired effects. It is believed thatby using the invention described herein, manufactures can be produced ata lower cost, while maintaining most, if not all, of the uniqueproperties of polymers produced with metallocene catalysts.

Additionally, these manufactures can be part of a machine, such as, forexample, a car, so that the weight of the car will be less, with theattended benefits thereof.

EXAMPLES

These examples provide additional information to a person skilled in theart. These examples are not meant to be construed as limiting the scopeof the claims.

Description of the Polymerizations Runs

All polymerization runs were conducted in a steel reactor that had avolume of 2.2 liters. This reactor was equipped with a marine stirrer.During the polymerizations this stirrer was set to run at 400 rpm. Thisreactor was also surrounded by a steel jacket that was connected to asteel condenser. The steel jacket contained methanol that was boiling.The boiling point of the methanol was controlled by varying the nitrogenpressure that was applied to the steel condenser and the steel jacket.This control method permitted precise temperature control (±0.5° C.).

First, a treated, or untreated, solid oxide compound was charged, undernitrogen, to the reactor, which was dry. Second, organometal compoundsolution was added to the reactor by syringe. Third, 0.6 liters ofisobutane was charged to the reactor. Fourth, organoaluminum compoundwas added midway during the isobutane addition. Fifth, 0.6 liters ofisobutane was charged to the reactor. Sixth, ethylene was added to thereactor to equal 550 psig pressure. Seventh, the reactor was heated to90° C. This pressure was maintained during the polymerization. Duringpolymerization, stirring continued for the specified time. Activity wasdetermined by recording the flow of ethylene into the reactor tomaintain pressure. Seventh, after the specified time, the ethylene flowwas stopped and the reactor slowly depressurized. Eighth, the reactorwas opened to recover a granular polymer powder.

In all inventive runs, the reactor was clean with no indication of anywall scale, coating or other forms of fouling. The polymer powder wasremoved and weighed. Activity was specified as grams of polymer producedper gram of treated, or untreated, solid oxide compound charged perhour.

In some cases the treated solid oxide compound and the organometalcompound were first pre-contacted, in the reactor, for about half anhour at 90° C. in one liter of isobutane before the organoaluminumcompound and ethylene were added to the reactor.

Preparation of Solid Oxides

Silica, grade 952, having a pore volume of 1.6 cc/g and a surface areaof about 300 square meters per gram was obtained from W. R. Grace. About10 grams of this material was placed in a 1.75 inch quartz tube, whichwas fitted at the bottom with a sintered quartz. While the silica wassupported on the disk, dry air was blown up through the disk at thelinear rate of about 1.6 to 1.8 standard cubic feet per hour. Anelectric furnace around the quartz tube was then turned on and thetemperature was raised at the rate of 400° C. per hour to a temperatureof 600° C. At that temperature, the silica was allowed to fluidize forthree hours in the dry air. Afterward, the silica was collected andstored under dry nitrogen.

Some alumina samples were also prepared by the procedure described inthe silica preparation. A commercial alumina sold by AKZO Company asKetjen grade B alumina was obtained, having a pore volume of about 1.78cc/g and a surface area of around 340 square meters per gram. Thetemperatures used in the preparation of these aluminas were 400° C.,600° C., and 800° C.

A silica-alumina was also obtained from W. R. Grace (MS 13-110containing 13% alumina and 87% silica). This silica-alumina had a porevolume of 1.2 cc/g and a surface area of about 300 square meters pergram. This silica-alumina was prepared as described in the silicapreparation. The temperature used in the preparation of thissilica-alumina was 600° C.

A silica-titania was obtained by co-gellation as described in U.S. Pat.No. 3,887,494 (“Deitz”). Titanyl sulfate was dissolved in concentratedsulfuric acid, to form a first mixture. Afterwards, a sodium silicatesolution was slowly added, with vigorous stirring, to this firstmixture, to form a second mixture. When the pH of the second mixturereached about 6, this second mixture gelled into a homogenous,substantially-clear first product. This first product was then aged, at80° C. and a pH 7, for three hours, followed by washing it nine timeswith water, and two times in 1% ammonium nitrate, to form a secondproduct. This second product, which was a gel, was then azeotropicallydried in ethyl acetate, to form a third product. This third productcontained 8%-titanium. It also had a surface area of 450 square metersper gram and a pore volume of 2.0 cc/g. This silica-titania was thenprepared as described in the silica preparation. The temperature use inthe preparation of this silica-titania was 600° C.

An alumino-phosphate was prepared according to U.S. Pat. No. 4,364,855(McDaniel). Aluminum nitrate (380 grams) and mono-ammonium phosphate (94grams) was dissolved in deionized water to form a first mixture. About170 milliliters of ammonium hydroxide was then added to this firstmixture to form a second mixture. At a pH of about 8 this second mixturegelled to form a first product. This first product was then washed twicein water, and once in n-propanol, before drying overnight at 80° C.under a vacuum, to form a second product. This second product containeda phosphorus to aluminum molar ratio of 0.8, a pore volume of 2.1 cc/g,and a surface area of 250 square meters per gram. This alumino-phosphatewas then prepared as described in the silica preparation. Thetemperature use in the preparation of this alumina-phosphate was 600° C.

Comparative Examples 1-2

These examples demonstrate that an organometal compound contacted withan organoaluminum compound, provides little, if any, polymerizationactivity.

A polymerization run was made as described earlier. First, anorganometal compound was added to the reactor (2 ml ofbis(n-butylcyclopentadienyl) zirconium dichloride solution containing0.5 grams per 100 ml of toluene). Second, half of the isobutane was thenadded to the reactor. Third, 2 ml of 15 weight percent triethyl aluminumfor example 1, or 2 ml of 25 weight percent ethyl aluminum dichloride(EADC) for example 2, were added to the reactor. Fourth, the other halfof the isobutane was added to the reactor.

Ethylene was then added to the reactor but no polymerization activitywas observed. After one hour of contacting, the reactor wasdepressurized and opened.

In each case, no polymer was found. These results are shown in Table-I.

Comparative Examples 3-9

These examples demonstrate that contacting a solid oxide compound, withan organometal compound, and with an organoaluminum compound, providedlittle, if any, polymerization activity.

Each of the solid oxide compounds described earlier was added to thereactor, followed by an organometal compound (2 ml ofbis(n-butylcyclopentadienyl) zirconium dichloride solution (0.5 gramsper 100 ml of toluene), and then the organoaluminum compound(triethylaluminum). These examples are shown in Table-I.

The first two examples show that contacting an organometal compound withan organoaluminum compound provides little, if any, polymerizationactivity. The silica example produced almost no polymer. Alumina, whichis regarded as more acidic than silica, produced more polymer, but stillthe activity was very low. The alumino-phosphate, silica-alumina, andsilica-titania supports exhibited only marginal activity. Activity isexpressed in Table-I as gP/(gS·hr).

Comparative Example 10

A solution was made of 244 grams of ammonium sulfate dissolved in waterto equal 437 mls total. Then 100 mls of this solution was impregnatedonto 33.2 grams of W. R. Grace grade 952 silica. The wet mixture wasdried in a vacuum oven at 110° C. for 12 hours. This is equivalent to12.7 mmol of sulfate per gram of silica. The dried material was groundthrough a 35 mesh screen, then calcined in air at 400° C. according tothe procedure described earlier. It was found to have a pore volume of1.22 cc/g and a surface area of 223 square meters per gram. A sample ofthis material was then tested for ethylene polymerization activity asdescribed earlier. It produced no polymer. This experiment is shown inTable II as example 10.

Examples 11-12

122 mls of the above ammonium sulfate solution was impregnated onto 40.6grams of Ketjen grade B alumina. The wet mixture was dried in a vacuumoven at 110° C. for 12 hours. This is equivalent to 12.7 mmol of sulfateper gram of uncalcined alumina. The dried material was then groundthrough a 35 mesh screen and calcined in air at 400° C. according to theprocedure described above. It was found to have a pore volume of only0.25 cc/g and a surface area of only 38 square meters per gram. A sampleof this material was then tested for ethylene polymerization activity asdescribed earlier. Despite the very low porosity it still produced 33g/g/h of polymer. This experiment is shown in Table II as example 11.

This same material was then calcined again in air at 750° C. asdescribed earlier, and retested for polymerization activity. This timeit provided 583 g/g/h of polymer. This is quite-remarkable consideringthe very low surface area. The polymer was found to have a melt index of0.15 and a high load melt index of 3.24. This experiment is shown inTable II as example 12.

Example 13A, B, C

Ketjen B alumina was first calcined in air at 600° C. as describedearlier. Then 11.1 grams of this material was slurried with 30 mls ofisopropanol mixed with 1.73 grams of sulfuric acid. This is equivalentto 1.6 mmol of sulfate per gram of calcined alumina. The isopropanol wasthen evaporated off under nitrogen with heat. The dry solid was thencalcined in air at 550° C. as described earlier. A sample of thismaterial was then tested for ethylene polymerization. It yielded 1387g/g/h of polymer. This experiment is shown in Table II as example 13A.

The earlier procedure Ketjen B alumina was first calcined in air at 600°C., then 5.9 grams of this material was slurried with 15 mls ofisopropanol mixed with 0.453 grams of sulfuric acid. This is equivalentto 1.6 mmol of sulfate per gram of calcined alumina. The isopropanol wasthen evaporated off under nitrogen with heat. The dry solid was thencalcined in air at 550° C. as described earlier. It was found to have apore volume of 0.93 cc/g and a surface area of 205 square meters pergram. A sample of this material was then tested for ethylenepolymerization. It yielded 324 g/g/h of polymer. This experiment isshown in Table II as example 13B.

This material was then calcined again at 800° C. for three hours in airas described earlier. It was found to have a pore volume of 1.03 cc/gand a surface area of 236 square meters per gram. It provided activityof 58 g/g/h polymer. This experiment is shown in Table II as example13C.

Examples 14A, B and 15

The procedure of example 11 was repeated except that 33.14 grams ofKetjen B alumina was impregnated with 11.60 grams of ammonium sulfateand then it was calcined at 550C. The results of testing are shown inTable II as example 14A. During this run the sulfated alumina andmetallocene were precontacted in the reactor for 32 minutes at 90Cbefore other ingredients were introduced to begin the run. Polymerproduced in this run was found to have a MI of 0.21, a HLMI of 3.5,giving a shear ratio of 16.7. Gel permeation chromatography of thepolymer indicated Mw=168,000, Mn=67,900 and Mw/Mn=2.5. After calciningthe sulfated alumina was found to have a surface area of 284 squaremeters per gram and a pore volume of 0.67 cc/g and an average poreradius of 94 angstroms.

The above sulfated alumina (14A) was then calcined in air at 650C forthree hours and tested again for polymerization. Again the sulfatedalumina and the metallocene werre precontacted for 30 minutes at 90C.Details of the run are shown in Table II as example 14B. This materialwas found to have a surface area of 305 square meters per gram, a porevolume of 0.9 cc/g, and an average pore volume of 110 angstroms.

Another sample of sulfated alumina was made by the same proceedure asexample 14A except that 26.9 g of Ketjen B alumina was inpreganated with5.41 g of ammonium sulfate. Calcination was at 550C. It was found tohave a surface area of 352 square meters per gram, a pore volume of 0.93cc/g, and an average pore radius of 106 angstroms. Details of thepolymertization are given in Table II as example 15.

Comparative Example 16

A solution of 2.0 grams of concentrated sulfuric acid in 200 mls ofisopropanol was made. Ketjen B alumina was calcined in air at 600° C. asdescribed earlier. Then 6.34 grams of this material was slurried with 16mls of the solution. This is equivalent to 0.26 mmol of sulfate per gramof calcined alumina. The isopropanol was then evaporated off undernitrogen with heat. The dry solid was then calcined in air at 500° C. asdescribed earlier. It was found to have a pore volume of 0.95 cc/g and asurface area of 213 square meters per gram. A sample of this materialwas then tested for ethylene polymerization. It yielded 6 g/g/h ofpolymer. This experiment is shown in Table II as example 16.

Example 17

A silica-alumina was obtained from W. R. Grace under the commercial nameof MS13-110. It's properties and activity have already been describedearlier. It was impregnated with sulfuric acid as described above inexample 16 to contain 1.6 mmol sulfate per gram. It was then calcined inair at 600° C. as described earlier. A sample of this material was thencharged to the reactor along with the metallocene and isobutane andstirred for 32 minutes at 90° C. before ethylene was added. It yielded82 g/g/h of polymer. This experiment is shown in Table II as example 17.

Example 18

A solution of 0.5 grams of ammonium bifluoride in 30 m/s of methanol wasadded to 4.5 grams of Ketjen grade B alumina which had been calcined inair at 600° C. as described earlier. This moistened the alumina justbeyond the point of incipient wetness. This is equivalent to 3.90 mmolof fluoride per gram of calcined alumina. The methanol was thenevaporated off under nitrogen with heat. The dry solid was then calcinedin nitrogen at 500° C. as described earlier. A sample of this materialwas then tested for ethylene polymerization. It yielded 927 g/g/h ofpolymer. This experiment is shown in Table III as example 18.

Examples 19-21

The procedure described in example 18 was repeated except that the finalcalcination was accomplished at 250° C., 400° C., and 600° C. Each wastested for polymerization activity and the results are shown in TableIII as examples 19, 20, and 21.

Example 22

The procedure described in example 18 was repeated except thatuncalcined Ketjen B alumina was impregnated with 5.80 mmol per gram offluoride. After calcination at 500° C. it was tested for polymerizationactivity and the result are shown in Table III as example 22.

Example 23-24

W. R. Grace grade HPV alumina was calcined at 600° C. in air threehours, giving a material of surface area around 500 square meters pergram and pore volume of about 2.8 cc/g. 3.36 grams of this material washeated under fluidizing nitrogen to 600° C. Then 5.0 mls ofperfluorohexane was injected into the nitrogen upstream from thealumina. Over the next 15 minutes the perfluorohexane evaporated at roomtemperature into the nitrogen and was then carried up through thefluidizing bed of alumina, where it reacted. This exposure would beequivalent to about 55 mmol of fluoride per gram of alumina if all ofthe fluoride reacted (which was obviously not the case). The aluminaturned black presumably due to carbon deposited on it. This material wasthen tested for polymerization activity when a sample was charged to thereactor with the metallocene at 90° C. After 30 minutes of stirring,triethyl aluminum and ethylene were added and the sample was found toprovide 1266 g/g/h of polymer. Details are shown in Table III as example23.

This material was then recalcined in air at 600° C. for three hours toburn off residual carbon. The black color turned back to white. It wasthen tested for polymerization activity when a sample of it was added tothe reactor along with metallocene and triethyl aluminum, followedimmediately by ethylene. It provided an activity of 2179 g/g/h ofpolymer. Details are shown in Table III as example 24.

Examples 25-26

Ketjen Grade B alumina was calcined in air for three hours at 600° C. asdescribed in example 5. 9.29 grams of this alumina was charged to a dryquartz activator tube and fluidized in carbon monoxide at 600° C. Then4.5 m/s of methyl bromide was injected upstream into the carbonmonoxide. During the next 30 minutes the methyl bromide was warmed withan electric heater causing it to evaporate and be carried by the carbonmonoxide gas through the fluidizing alumina bed at 600° C. After thistreatment the alumina was black, presumably from carbon deposits. Asample was tested for polymerization activity and found ta give 223g/g/h of polymer. In a second similar run it was found to give 181 g/g/hof polymer. These two runs are shown in Table IV as examples 25 and 26.

Example 27

Ketjen Grade B alumina was calcined in air for three hours at 600° C. asdescribed in example 5. 9.82 grams of this alumina was charged to a dryquartz activator tube and fluidized in carbon monoxide at 600° C. Then1.0 mls of bromine liquid was injected upstream into the carbon monoxidewhich slowly evaporated and was carried through the fluidizing aluminabed at 600° C. After this treatment the alumina was white. A sample wastested for polymerization activity and found to give 106 g/g/h ofpolymer. This run is shown in Table IV as example 27.

Examples 28-31

Ten mls of Ketjen Grade B alumina was calcined in air for three hours at600° C. as described in example 5. After this calcining step, thefurnace temperature was lowered to 400° C. and 1.0 ml of carbontetrachloride was injected into the nitrogen stream and evaporatedupstream from the alumina bed. It was carried into the bed and therereacted with the alumina to chloride the surface. This is equivalent toapproximately 15.5 mmol chloride per gram of dehydrated alumina. Afterthis treatment the alumina was white. A sample was tested forpolymerization activity. In addition to the ethylene, 50 mls of 1-hexenewas also added to the reactor as a comonomer. This material gave 939g/g/h of copolymer having the following properties: melt index of 0.63,high load melt index of 10.6, shear ratio of 16.7, density of 0.9400,weight average MW of 126,000, number average MW of 50,200, andpolydispersity of 2.5. This run in shown in Table V as example 28.

This chlorided alumina was run again but without the hexene and thedetails are shown in Table V as example 29. It produced 1019 g/g/h ofpolymer having the following properties: melt index of 0.15, high loadmelt index of 2.68, shear ratio of 17.9, density of 0.9493, weightaverage MW of 202,000, number average MW of 62,400, and polydispersityof 3.2.

In a similar experiment, 7.3 grams of Ketjen Grade B alumina alreadycalcined at 600° C. in air, was treated with 0.37 mls of carbontetrachloride vapor in nitrogen at 400° C. This is equivalent toapproximately 2.4 mmol chloride per gram of calcined alumina. Thismaterial provided 146 g/g/h activity and is shown in Table V as example30.

In yet another similar experiment, the procedure of example 29 wasrepeated except that 6.2 grams of 600° C. calcined alumina was treatedwith 5.0 mls of carbon tetrachloride at 400° C., which is approximatelyequivalent to 37.6 mmol chloride per gram. This material yielded 1174g/g/h activity and is shown in Table V as example 31.

Examples 32-35

Three other samples of Ketjen Grade B alumina were also calcined at 600°C. in air as described in the above examples and then treated withvarious amounts of carbon tetrachloride at various temperatures. Table Vshows the results of these experiments as examples 32, 33, and 34. Inexample 33 the treatment was done in carbon monoxide gas instead ofnitrogen.

The catalyst of example 33 was retested for polymerization activity butwith the following variation. Instead of charging all ingredients to thereactor and immediately starting the run, the oxide and the metalloceneto were charged with the isobutane first and allowed to contact eachother for 37 minutes at 90° C. before the cocatalyst and ethylene wereadded to begin the run. This run is shown in Table V as example 35.

Example 36

W. R. Grace Grade HPV alumina was calcined in air for three hours at600° C., yielding a surface area of approximately 500 square meters pergram and a pore volume of about 2.8 cc/g. 5.94 grams of this alumina wasthen treated with 5.0 mls of carbon tetrachloride in nitrogen at 600° C.Results of polymerization testing are shown in Table V as example 36.

Example 37

W. R. Grace Grade MS13-110 silica-alumina was calcined in air for threehours at 600° C., as described in example 8 above. 11.2 grams thentreated with 2.8 mls of carton tetrachloride in nitrogen at 600° C.Results of polymerization testing are shown in Table V as example 37.

Example 38

6.96 grams of Ketjen Grade B alumina which had been calcined at 400° C.in air for three hours was charged to a dry activator tube and heatedunder nitrogen to 400° C. 2.1 mls of silicon tetrachloride was theninjected into the nitrogen upstream from the alumina. As it evaporatedit was carried up through the alumina bed, reacting and chloriding thesurface. When tested for polymerization activity this material provided579 g/g/h of polymer having a melt index of 0.20, a high load melt indexof 3.58, and a shear ratio of 17.9. Details of the polymerization testare shown in Table VI as example 38.

Example 39

8.49 grams of Ketjen Grade B alumina which had been calcined at 600° C.in air for three hours was charged to a dry activator tube and heatedunder nitrogen to 300° C. 2.8 mls of thionyl chloride was then injectedinto the nitrogen upstream from the alumina. As it evaporated it wascarried up through the alumina bed, reacting and chloriding the surface.When tested for polymerization activity this material provided 764 g/g/hof polymer having a melt index of 0.13, a high load melt index of 2.48,and a shear ratio of 18.6. Details of the polymerization test are shownin Table VI as example 39.

Example 40

7.63 grams of Ketjen Grade B alumina which had been calcined at 400° C.in air for three hours was charged to a dry activator tube and heatedunder dry air to 300° C. 2.55 mls of sulfuryl chloride was then injectedinto the air upstream from the alumina. As it evaporated over a periodof about 45 minutes at room temperature it was carried up through thealumina bed, reacting and chloriding the surface. When tested forpolymerization activity this material provided 459 g/g/h of polymerhaving a melt index of 0.11, a high load melt index of 2.83, and a shearratio of 25.6. Details of the polymerization test are shown in Table VIas example 40.

Comparative Examples 41-43 and Examples 44-45

2.6955 grams of solid aluminum trichloride was added to the reactoralong with 2.0 m/s of 15% triethyl aluminum and 2.0 mls of themetallocene solution used in previous experiments. Isobutane andethylene were added as in previous runs. However, no activity wasobserved. This run is summarized in Table 6 as example 41. Theexperiment was then repeated but with less aluminum trichloride in thereactor, but again no activity was observed. This was example 42. ThusAlC13 itself does not function as an activator for metallocenes. Thereis a distinct difference between aluminum trichloride and chloridedalumina.

In the following example aluminum trichloride was deposited onto thesurface of dehydrated alumina in order to give it a higher surface area.1.4 grams of anhydrous aluminum trichloride was dissolved in 100 mls ofdichloromethane. This solution was then added to 6 grams of Ketjen GradeB alumina which had been calcined at 600° C. in air for three hours. Thedichloromethane was evaporated under nitrogen at 60° C. A sample of thismaterial was then tested for polymerization activity (example 43) but ithad little. The material was then heated under nitrogen to 250° C. forone hour and retested for polymerization activity (example 44). Thistime some activity was detected. Next the material was again heatedunder nitrogen to 400° C. for one hour and retested for polymerizationactivity (example 45) and activity was observed.

Comparative Examples 46 and 48 and Example 47

In another experiment 3.5 grams of Ketjen Grade B alumina calcined at600° C. was treated with 10 mls of 25% ethyl aluminum dichloride (EADC)at 60° C. for 10 minutes, then rinsed twice to remove any unreactedEADC. When tested for polymerization activity (first without, then withcocatalyst), none was observed (example 46). The material was thenheated under nitrogen for 1 hour at 200° C. and retested (example 47).Some activity was observed.

In a similar experiment 4.31 grams of Ketjen Grade B alumina calcined at400° C. was treated with 30 mls of 25 wt % diethyl aluminum chloride(DEAC) at 90° C. for 30 minutes. The excess DEAC was decanted and thesolid washed three times in dry heptane. It was then dried at 100° C.under nitrogen and tested for polymerization activity (example 48). Itexhibited 29 .g/g/h activity.

Comparative Example 49

A 2.26 gram sample of Davison 952 silica which had previously beencalcined in dry air for three hours at 600° C. was impregnated to thepoint of incipient wetness with 3.4 mls of trifluoromethane sulfonicacid (95.7% pure). The procedure was done under nitrogen in a flask.This material was then mixed with 8.96 grams of Ketjen Grade B aluminawhich had previously been calcined in dry air for three hours at 600° C.The resulting solid material as 79.9% by weight alumina, 29.1% by weightsilica. This procedure was done in a dry activator tube on a fluidizedbed in nitrogen. The mixture was heated to 193° C.-230° C. for threehours in nitrogen to allow the trifluoromethane sulfonic acid toevaporate and react with the alumina, which would give atriflouromethane sulfonic acid loading of 1 millimole per gram of thealumina. It was then tested for polymerization activity as describedabove except that the ethylene pressure was set at 450 psig instead of550 psig and 25 mls of 1-hexene was added to the reactor. Results areshown in Table VII.

Example 50

The solid oxide from example 49 was then heated under nitrogen to 400°C. for an additional three hours to further encourage distribution andreaction of the triflic acid. It was then tested for polymerizationactivity as described above except that the ethylene pressure was set at450 psig instead of 550 psig and 25 mls of 1-hexene was added to thereactor. Results are shown in Table VII.

Example 51

The solid oxide from example 50 was again heated under nitrogen to 600°C. for an additional three hours to further encourage distribution ofthe triflic acid. It was then tested for polymerization activity asdescribed above except that the ethylene pressure was set at 450 psiginstead of 550 psig and 25 mls of 1-hexene was added to the reactor.Results are shown in Table VII.

Example 52

A solution of 0.5 grams of ammonium bifluoride was dissolved in 30 mlsof methanol and deposited onto a 4.5 gram sample of Ketjen Grade Balumina which had been calcined at 600° C. for three hours in air. Thisbrought the solid just beyond the point of incipient wetness. Themethanol was then evaporated off under a nitrogen purge on a hot plateand then transferred to an activator tube, where it was heated undernitrogen to 500° C. and held 2 hours. 1.89 grams of this material wasthen treated at 500C under nitrogen with 0.5 m/s of carbon tetrachlorideinjected into the gas stream. A sample was then tested forpolymerization activity with metallocene and 2.0 mls of triethylaluminum cocatalyst. It generated 3132 g/g/h of polymer. Details arelisted in Table VIII.

Example 53-54

6.18 grams of W. R. Grace Grade HPV alumina which had been calcined at600° C. for three hours in air yielding a surface area of approximately500 square meters per gram and a pore volume of about 2.8 cc/g, wastransferred to a dry activator tube and heated under nitrogen to 600° C.0.24 m/s of perfluorohexane was then injected into the nitrogen streamahead of the furnace. The liquid evaporated and was carried up throughthe alumina bed, fluoriding its surface. Then 1.55 mls of carbontetrachloride was injected into the nitrogen stream and carried into thealumina bed at 600° C. The temperature was cooled to 25° C. and theresultant fluorided-chlorided alumina was stored under nitrogen. A smallsample of this material was then tested for polymerization activity withmetallocene and triethyl aluminum. The activity, shown in example 53,was quite high, at 4390 g/g/h.

This material was then run again except that it was allowed to stir inisobutane with the metallocene at 90° C. for 30 minutes before the otheringredients were added. This procedure yielded 6298 g/g/h activity(example 54).

Example 55

Degussa Aluminoxid C, obtained by flame hydrolysis, was calcined at 600°C. in air for three hours. Then 2.74 grams of this calcined alumina washeated to 600° C. in air, into which 4.1 mls of perfluorohexane wasinjected. As the liquid evaporated, it was carried up by the air throughthe alumina bed. Afterwards the gas stream was switched from air tonitrogen and 1.0 ml of carbon tetrachloride was injected. After all hadevaporated, the solid was cooled to room temperature and stored underdry nitrogen. A small sample was tested for polymerization activity withmetallocene and cocatalyst as previously described. This material wasfound to yield 1383 g/g/h. Details are recorded in Table VIII.

Examples 56, 60-61, 63-64 and Comparative Examples 57-59, 62, 65-66

A chlorided alumina was prepared identically to that in example 33. Ineach experiment a sample of the oxide was added to the reactor undernitrogen, then 2 mis of a solution of 0.5 grams of bis(n-butylcyclopentadienyl) zirconium dichloride in 100 mls of toluene was added,then 0.6 liter of isobutane liquid, then 1 mmol of the cocatalyst(usually from a hexane solution) followed by another 0.6 liter ofisobutane, and finally the ethylene was added after the reactor reached90° C. Table IX shows the results of these experiments as examples 56through 62.

A similar comparison of cocatalysts was made using an alumina which hadbeen fluorided rather than chlorided according to the preparation usedin example 21. These runs are shown in Table IX in examples 63 through66.

Examples 67-71

In each run below the fluorided chlorided alumina used in example 50 wascharged to the reactor, followed by 2 mis of a solution of 0.5 grams ofthe selected metallocene in, 100 mls of toluene, followed by 0.6 literof isobutane liquid, then 2.0 mls of 1M triethyl aluminum as cocatalyst,followed by another 0.6 liters of isobutane and finally the ethylene.These runs were made at 90° C., like all previous runs. Details areshown in Table X.

TABLE I Ex. # A¹ ° C.² S³ OAC⁴ P⁵ T⁶ A⁷ 1⁸ None NA 0.0000 2 TEA 0 61.1 02 None NA 0.0000 2 EADC 0 28.0 0 3 Silica 600 0.5686 2 TEA 0.65 63.0 1 4Alumina 800 0.6948 1 TEA 2.7 30.7 8 5 Alumina 600 0.2361 2 TEA 6.9 60.929  6 Alumina 400 0.8475 1 TEA trace 57.2 0 7 Alumino- 600 0.8242 1 TEA45 66.0 50  Phosphate (0.8) 8 Silica-Alumina 600 0.3912 1 TEA 8.3 40.032  9 Silica-Titania 600 0.1392 2 TEA 0 60.0 0 Table I Notes ¹This isthe untreated solid oxide compound used. ²This is the calciningtemperature. ³This is the amount of solid oxide compound, in grams,being contacted with the other compounds. ⁴This is the amount, inmilliliters of organoaluminum compound used and the type oforganoaluminum used. The TEA was a 15 weight percent solution oftriethylaluminum in heptane. ⁵This is the amount of polymer produced ingrams. ⁶This is the amount of time used in minutes. ⁷This is theactivity in gP/(gS*hr). ⁸The amount of organometal compound used was 25micromoles. The type of organometal compound used wasbis(n-butylcyclopentadienyl) zirconium dichloride. This organometalcompound was in a solution that contained 0.5 grams ofbis(n-butylcyclopentadienyl) zirconium dichloride per 100 milliliters oftoluene. Additionally, these example were run at 90° C., under 550 psigethylene, in 1.2 liters of isobutane.

TABLE II Ex. # A¹ S² ° C.³ S⁴ OAC⁵ P⁶ T⁷ A⁷ 10⁹ Silica 12.7 400 1.3360 20 30.0 0 11 Alumina 12.7 400 1.5251 2 38.0 45.0 33 12 Alumina 12.7 7500.2994 2 174.5 60.0 583 13A Alumina 1.6 550 0.3474 1 385.5 48.0 1387 13BAlumina 0.8 550 0.7468 2 242.0 60.0 324 13C Alumina 0.8 800 0.8004 234.8 45.0 58 14A Alumina 2.7 550 0.0842 2 241 60 2862 14B Alumina 2.7650 0.0801 2 203 60 2534 15 Alumina 1.5 550 0.0279 2 90 60 3226 16Alumina 0.26 500 0.7749 2 2.3 30.0 6 17 Silica- 1.6 600 0.3318 1 19.042.0 82 Alumina Table II Notes ¹This is the solid oxide compound used.²This is the amount of sulfate used in mmols sulfate per gram of solidoxide. ³This is the calcining temperature. ⁴This is the amount of solidoxide compound, in grams, being contacted with the other compounds.⁵This is the amount, in milliliters, of TEA used. It was a 15 weightpercent solution of triethylaluminum in heptane. ⁶This is the amount ofpolymer produced in grams. ⁷This is the amount of time used in minutes.⁸This is the activity in gP/(gS*hr). ⁹The amount of organometal compoundused was 25 micromoles. The type of organometal compound used wasbis(n-butylcyclopentadienyl) zirconium dichloride. This organometalcompound was in a solution that contained 0.5 grams ofbis(n-butylcyclopentadienyl) zirconium dichloride per 100 milliliters oftoluene. Additionally, these example were run at 90° C., under 550 psigethylene, in 1.2 liters of isobutane.

TABLE III Ex. # A¹ S² ° C.³ S⁴ OAC⁵ P⁶ T⁷ A⁸ 18⁹ Alumina 3.90 500 0.82842 296.8 23.2 927 19 Alumina 3.90 250 0.2542 2 7.6 40.0 45 20 Alumina3.90 400 0.2358 2 88.1 60.0 374 21 Alumina 3.90 600 0.2253 2 281.6 60.01250 22 Alumina 5.80 500 0.2563 1 243.9 60.0 952 23 Alumina 55 5000.2212 1 280.0 60.0 1266 24 Alumina 55 600 0.0855 1 187.5 60.5 2179Table III Notes ¹This is the solid oxide compound used. ²This is theamount of fluoride used in mmols fluoride per gram of solid oxide. ³Thisis the calcining temperature. ⁴This is the amount of solid oxidecompound, in grams, being contacted with the other compounds. ⁵This isthe amount, in milliliters, of TEA used. It was a 15 weight percentsolution of triethylaluminum in heptane. ⁶This is the amount of polymerproduced in grams. ⁷This is the amount of time used in minutes. ⁸This isthe activity in gP/(gS*hr). ⁹The amount of organometal compound used was25 micromoles. The type of organometal compound used wasbis(n-butylcyclopentadienyl) zirconium dichloride. This organometalcompound was in a solution that contained 0.5 grams ofbis(n-butylcyclopentadienyl) zirconium dichloride per 100 milliliters oftoluene. Additionally, these example were run at 90° C., under 550 psigethylene, in 1.2 liters of isobutane.

TABLE IV Ex. # A¹ ° C.² S³ OAC⁴ P⁵ T⁶ A⁷ 25⁸ Alumina 600 0.2612 1 62.064.0 223 26 Alumina 600 0.1688 1 38.0 74.6 181 27 Alumina 600 0.2046 111.9 33.0 106 Table IV Notes ¹This is the solid oxide compound used.²This is the calcining temperature. ³This is the amount of solid oxidecompound, in grams, being contacted with the other compounds. ⁴This isthe amount, in milliliters, of TEA used. It was a 15 weight percentsolution of triethylaluminum in heptane. ⁵This is the amount of polymerproduced in grams. ⁶This is the amount of time used in minutes. ⁷This isthe activity in gP/(gS*hr). ⁸The amount of organometal compound used was25 micromoles. The type of organometal compound used wasbis(n-butylcyclopentadienyl) zirconium dichloride. This organometalcompound was in a solution that contained 0.5 grams ofbis(n-butylcyclopentadienyl) zirconium dichloride per 100 milliliters oftoluene. Additionally, these example were run at 90° C., under 550 psigethylene, in 1.2 liters of isobutane.

TABLE V Ex. # A¹ S² ° C.³ S⁴ OAC⁵ P⁶ T⁷ A⁸ 28⁹ Alumina 15.5 400 0.1596 2149.8 60.0  939 29 Alumina 15.5 400 0.1166 2 121.8 61.5 1019 30 Alumina2.4 400 0.2157 2 28.8 55.0  146 31 Alumina 37.6 400 0.1021 2 123.9 62.01174 32 Alumina 11.7 250 0.4878 2 39.2 60.0  80 33 Alumina 11.7 6000.2058 2 351.5 63.0 1627 34 Alumina 38.2 800 0.0488 1 30.6 46.5  809 35Alumina 11.7 600 0.1505 1 400.0 62.0 2572 36 Alumina 39.3 600 0.0927 1260.2 60.0 2807 37 Silica- 11.7 600 0.0667 1 147.8 60.5 2198 AluminaTable V Notes ¹This is the solid oxide compound used. ²This is theamount of chloride used in mmols chloride per gram of solid oxide. ³Thisis the calcining temperature. ⁴This is the amount of solid oxidecompound, in grams, being contacted with the other compounds. ⁵This isthe amount, in milliliters, of TEA used. It was a 15 weight percentsolution of triethylaluminum in heptane. ⁶This is the amount of polymerproduced in grams. ⁷This is the amount of time used in minutes. ⁸This isthe activity in gP/(gS*hr). ⁹The amount of organometal compound used was25 micromoles. The type of organometal compound used wasbis(n-butylcyclopentadienyl) zirconium dichloride. This organometalcompound was in a solution that contained 0.5 grams ofbis(n-butylcyclopentadienyl) zirconium dichloride per 100 milliliters oftoluene. Additionally, these example were run at 90° C., under 550 psigethylene, in 1.2 liters of isobutane.

TABLE VI Ex. # A¹ Treatment S² OAC³ P⁴ T⁵ A⁶ 38⁷ Alumina SiCl4 - 400° C.0.2013 1 116.5 60.0 579 39 Alumina SOCl2 - 0.0793 1 62.0 61.4 764 300°C. 40 Alumina SO2Cl2 - 0.3915 1 186.0 62.1 459 300° C. 41 none AlCl3solid 2.6955 2 0 30.0  0 42 none AlCl3 solid 0.0380 2 0 34.4  0 43Alumina AlCl3 - 80° C. 0.4264 2 4.3 28.0  22 44 Alumina AlCl3 - 0.3374 2135.3 60.0 401 250° C. 45 Alumina AlCl3 - 0.2335 1 74.9 60.0 322 400° C.46 Alumina EtAlCl2 - 0.8855 2 0 30.0  0 60° C. 47 Alumina EtAlCl2 -0.8943 2 122.9 49.0 168 200° C. 48 Alumina Et2AlCl - 0.4263 1 4.9 24.0 29 90° C. ¹This is the solid oxide compound used. ²This is the amountof solid oxide compound, in grams, being contacted with the othercompounds. ³This is the amount, in milliliters, of TEA used. It was a 15weight percent solution of triethylaluminum in heptane. ⁴This is theamount of polymer produced in grams. ⁵This is the amount of time used inminutes. ⁶This is the activity in gP/(gS*hr). ⁷The amount of organometalcompound used was 25 micromoles. The type of organometal compound usedwas bis(n-butylcyclopentadienyl) zirconium dichloride. This organometalcompound was in a solution that contained 0.5 grams ofbis(n-butylcyclopentadienyl) zirconium dichloride per 100 milliliters oftoluene. Additionally, these example were run at 90° C., under 550 psigethylene, in 1.2 liters of isobutane.

TABLE VII Ex. # A¹ S² ° C.³ S⁴ OAC⁵ P⁶ T⁷ A⁸ 49 Alumina 1.0 200 .0868 11.5 80.5  13 50 Alumina 1.0 400 .1530 1 95.1 60.5  616 51 Alumina 1.0600 .0467 1 51.1 60.2 1090 Table VII Notes ¹This is the solid oxidecompound used. ²This is the amount of triflate used in mmols triflateper gram of solid oxide. ³This is the calcining temperature. ⁴This isthe amount of solid oxide compound, in grams, being contacted with theother compounds. ⁵This is the amount, in milliliters, of TEA used. Itwas a 15 weight percent solution of triethylaluminum in heptane. ⁶Thisis the amount of polymer produced in grams. ⁷This is the amount of timeused in minutes. ⁸This is the activity in gP/(gS*hr). ⁹The amount oforganometal compound used was 25 micromoles. The type of organometalcompound used was bis(n-butylcyclopentadienyl) zirconium dichloride.This organometal compound was in a solution that contained 0.5 grams ofbis(n-butylcyclopentadienyl) zirconium dichloride per 100 milliliters oftoluene. Additionally, these example were run at 90° C., under 450 psigethylene, in 1.2 liters of isobutane, and in 25 mls of 1-hexene.

TABLE VIII EX. # A¹ Treatment S² OAC³ P⁴ R⁵ A⁶ 52⁷ Alumina F/500C &0.2822 2 294.6 20.0 3132 Cl/500C 53 Alumina F/600C & 0.0767 2 338.4 60.34390 Cl/600C 54 Alumina F/600C 0.0967 2 304.5 30.0 6298 Cl/600C 55Alumina F/600C & 0.1196 1 174.2 63.2 1383 Cl/600C Table VIII Notes ¹Thisis the solid oxide compound used. ²This is the amount of solid oxidecompound, in grams, being contacted with the other compounds. ³This isthe amount, in milliliters, of TEA used. It was a 15 weight percentsolution of triethylaluminum in heptane. ⁴This is the amount of polymerproduced in grams. ⁵This is the amount of time used in minutes. ⁶This isthe activity in gP/(gS*hr). ⁷The amount of organometal compound used was25 micromoles. The type of organometal compound used wasbis(n-butylcyclopentadienyl) zirconium dichloride. This organometalcompound was in a solution that contained 0.5 grams ofbis(n-butylcyclopentadienyl) zirconium dichloride per 100 milliliters oftoluene. Additionally, these example were run at 90° C., under 550 psigethylene, in 1.2 liters of isobutane.

TABLE IX Ex. # A¹ Treatment S² CC³ P⁴ T⁵ A⁶ 56⁷ Alumina Chlorided 0.1866AlEt3 336.0 60.0 1800 57 Alumina Chlorided 0.1958 GaMe3 0 60.0 0 58Alumina Chlorided 0.1878 ZnEt2 0 60.0 0 59 Alumina Chlorided 0.1756MgBu2 2.5 60.0 14 60 Alumina Chlorided 0.1966 AlEt2H 52.6 60.0 268 61Alumina Chlorided 0.1777 Al(T-Bu)3 293 60.0 1649 62 Alumina Chlorided0.1840 LiHex 0 60.0 0 63 Alumina Fluorided 0.2253 AlEt3 281.6 60.0 125064 Alumina Fluorided 0.2181 AlMe3 154.2 60.0 707 65 Alumina Fluorided0.2307 AlEt2Cl 0 40.0 0 66 Alumina Fluorided 0.2465 BEt3 0 30.0 0 TableIX Notes ¹This is the solid oxide compound used. ²This is the amount ofsolid oxide compound, in grams, being contacted with other compounds.³This is the amount, in milliliters, of cocatalyst used. ⁴This is theamount of polymer produced in grams. ⁵This is the amount of time used inminutes. ⁶This is the activity in gP/(gS*hr). ⁷The amount of organometalcompound used was 25 micromoles. The type of organometal compound usedwas bis(n-butylcyclopentadienyl) zirconium dichloride. This organometalcompound was in a solution that contained 0.5 grams ofbis(n-butylcyclopentadienyl) zirconium dichloride per 100 milliliters oftoluene. Additionally, these example were run at 90° C., under 550 psigethylene, in 1.2 liters of isobutane.

TABLE X Ex. # A¹ Treatment S² Metallocene⁶ P³ T⁴ A⁵ 67 Alumina F/Cl 600C0.0212 A 141.3 63.3 6318 68 Alumina F/Cl 600C 0.0170 B 31.1 66.3 1656 69Alumina F/Cl 600C 0.0213 C 15.8 64.2  693 70 Alumina F/Cl 600C 0.1000 D83.9 61.5  819 Table IX Notes ¹This is the solid oxide compound used.²This is the amount of solid oxide compound, in grams, being contractedwith the other compounds. ³This is the amount of polymer produced ingrams. ⁴This is the amount of time used in minutes. ⁵This is theactivity in gP/(gS*hr). ⁶A = bis(n-butylcyclopentadienyl) zirconiumdichloride B = bis(cyclopentadienyl) zirconium dichloride C =bis(cyclopentadienyl) hafnium dichloride D =bis(n-butylcyclopentadienyl) zirconium chloride trimethylsilysmethyl

What is claimed is:
 1. A process of using a catalyst composition topolymerize at least one monomer to produce a polymer, said processcomprising contacting said catalyst composition and at least one monomerin a polymerization zone under polymerization conditions to produce saidpolymer; wherein said catalyst composition is produced by a processcomprising contacting at least one organometal compound, at least onetreated solid oxide compound, and at least one organoaluminum compoundto produce said catalyst composition, wherein said organometal compoundhas the following general formula (X¹)(X²)(X³)(X⁴)M¹ wherein M¹ isselected from titanium, zirconium, or hafnium, and wherein (X¹) isindependently selected from cyclopentadienyls, indenyls, fluorenyls,substituted cyclopentadienyls, substituted indenyls, or substitutedfluorenyls, and wherein substituents on said substitutedcyclopentadienyls, substituted indenyls, and substituted fluorenyls areselected from aliphatic groups, cyclic groups, combinations of aliphaticand cyclic groups, organometallic groups, or hydrogen; and wherein (X³)and (X⁴) are independently selected from halides, aliphatic groups,cyclic groups, combinations of aliphatic and cyclic groups, ororganometallic groups, and wherein (X²) is selected fromcyclopentadienyls, indenyls, fluorenyls, substituted cyclopentadienyls,substituted indenyls, substituted fluorenyls, halides, aliphatic groups,cyclic groups, combinations of aliphatic and cyclic groups, ororganometallic groups, and wherein said organoaluminum compound has thefollowing general formula, Al(X⁵)_(n)(X⁶)_(3-n) wherein (X⁵) is ahydrocarbyl having from 1-20 carbon atoms, and wherein (X⁶) is a halide,hydride, or alkoxide, and wherein “n” is a number from 1 to 3 inclusive;wherein said treated solid oxide compound is produced by a processcomprising contacting at least one solid oxide compound with at leastone electron-withdrawing anion source compound; and wherein said solidoxide compound is calcined before, during, or after contacting saidelectron-withdrawing anion source; and wherein the activity of saidcatalyst composition is greater than 250 grams of polyethylene per gramof treated solid oxide compound per hour; and wherein there is asubstantial absence of aluminoxanes and organoborates.
 2. A processaccording to claim 1, wherein said polymerization conditions compriseslurry polymerization conditions.
 3. A process according to claim 2,wherein said contacting is conducted in a loop reactor zone.
 4. Aprocess according to claim 3, wherein said contacting is conducted inthe presence of a diluent that comprises, in major part, isobutane.
 5. Aprocess according to claim 2, wherein said at least one monomer isethylene.
 6. A process according to claim 2, wherein said at least onemonomer comprises ethylene and an aliphatic 1-olefin having 3 to 20carbon atoms per molecule.
 7. A process according to claim 1, whereinsaid treated solid oxide compound is produced by a processcomprising: 1) contacting said solid oxide compound with said at leastone electron-withdrawing anion source compound to form a first mixture;and 2) calcining said first mixture to form said treated solid oxidecompound.
 8. A process according to claim 1, wherein said treated solidoxide compound is produced by a process comprising simultaneouslycalcining and contacting said solid oxide compound and said at least oneelectron-withdrawing anion source compound.
 9. A process according toclaim 1, wherein said electron-withdrawing anion source compound isselected from sulfates, halides, or triflate.
 10. A process according toclaim 1, wherein said calcining is conducted for about 1 hour to about10 hours at a temperature in the range of about 400° C. to about 800° C.11. A process according to claim 1, wherein said treated solid oxidecompound is produced by a process comprising increasing the acidity ofsaid solid oxide compound by two, or more, electron-withdrawing anionsource compounds in two, or more, separate steps.
 12. A processaccording to claim 11, wherein said treated solid oxide compound isproduced by a process comprising: 1) contacting said at least one solidoxide compound with a first electron-withdrawing anion source compoundto form a first mixture; 2) calcining said first mixture to produce acalcined first mixture; 3) contacting said calcined first mixture with asecond electron-withdrawing anion source compound to form a secondmixture; and 4) calcining said second mixture to form said treated solidoxide compound.
 13. A process according to claim 1, wherein saidcatalyst composition is produced by a process comprising: 1) contactingsaid organometal compound and said treated solid oxide compound togetherfor about 1 minute to about 1 hour at a temperature of about 25° C. toabout 100° C. to form a first mixture; and 2) contacting said firstmixture with an organoaluminum compound to form said catalystcomposition.
 14. A process according to claim 1, wherein said catalystcomposition can polymerize ethylene into a polymer with an activitygreater than 2000 (gP/(gS·hr)), and wherein said at least oneorganometal compound is selected from bis(cyclopentadienyl) hafniumdichloride; bis(cyclopentadienyl) zirconium dichloride;[ethyl(indenyl)₂] hafnium dichloride; [ethyl(indenyl)₂] zirconiumdichloride; [ethyl(tetrahydroindenyl)₂] hafnium dichloride;[ethyl(tetrahydroindenyl)₂] zirconium dichloride;bis(n-butylcyclopentadienyl) hafnium dichloride;bis(n-butylcyclopentadienyl) zirconium dichloride;((dimethyl)(diindenyl)silane) zirconium dichloride;((dimethyl)(diindenyl)silane) hafnium dichloride;((dimethyl)(ditetrahydroindenyl)silane) zirconium dichloride;((dimethyl)(di(2-methyl indenyl)) silane) zirconium dichloride;bis(fluorenyl) zirconium dichloride; or mixtures thereof, and whereinsaid at least one organoaluminum compound is selected fromtrimethylaluminum; triethylaluminum; tripropylaluminum; diethylaluminumethoxide; tributylaluminum; triisobutylaluminum hydride;triisobutylaluuminum; diethylaluminum chloride; or mixtures thereof, andwherein said solid oxide compound is selected from Al₂O₃, B₂O₃, BeO,Bi₂O₃, CdO, Co₃O₄, Cr₂O₃, CuO, Fe₂O₃, Ga₂O₃, La₂O₃, Mn₂O₃, MoO₃, NiO,P₂O₅, Sb₂O₅, SiO₂, SnO₂, SrO, ThO₂, TiO₂, V₂O₅, WO₃, Y₂O₃, ZnO, ZrO₂;mixed oxides thereof, or mixtures thereof, and wherein said treatedsolid oxide compound has been contacted with fluoride or chloride orboth.
 15. A process of using a catalyst composition to polymerize atleast one monomer to produce a polymer, said process comprisingcontacting said catalyst composition and said at least one monomer in apolymerization zone under polymerization conditions to produce saidpolymer; wherein said catalyst composition is produced by a processcomprising: 1) calcining alumina at about 600° C. for about 3 hours andsimultaneously contacting with carbon tetrachloride to produce a treatedsolid oxide compound; 2) combining said treated solid oxide compoundwith bis(n-butylcyclopentadienyl) zirconium chloride at a temperature ina range of about 25° C. to about 100° C. to produce a mixture; and 3)about between 1 minute and 1 hour, combining said mixture andtriethylaluminum to produce said catalyst composition.
 16. A process ofusing a catalyst composition to polymerize at least one monomer toproduce a polymer, said process comprising contacting said catalystcomposition and said at least one monomer in a polymerization zone underpolymerization conditions to produce said polymer; wherein said catalystcomposition is produced by a process comprising: 1) calcining an oxideselected from alumina, silica-alumina, aluminophosphate, and mixturesthereof to produce a calcined oxide; 2) contacting said calcined oxidewith a treating agent selected from sulfating agents, fluoriding agents,and chloriding agents to produce a treated oxide; 3) combining (1) saidtreated oxide, (2) an organoaluminum compound selected fromtriethylaluminum, triisobutylaluminum, and mixtures thereof; and (3) anorganometal compound, wherein said catalyst composition has an activitygreater than 100 gP/gS·hr in the substantial absence of aluminoxanes andorganoborates.
 17. A process according to claim 16, wherein saidorganometal compound is bis(n-butylcyclopentadienyl) zirconiumdichloride.
 18. A process according to claim 17, wherein said treatingagent is a chloriding agent.
 19. A process according to claim 18,wherein said treating agent is carbon tetrachloride.
 20. A process ofusing a catalyst composition to polymerize at least one monomer toproduce a polymer, said process comprising contacting said catalystcomposition and said at least one monomer in a polymerization zone underpolymerization conditions to produce said polymer; wherein said catalystcomposition is produced by a process comprising: 1) calcining alumina toproduce a calcined alumina; 2) treating said calcined alumina withcarbon tetrachloride at an elevated temperature to give a treatedalumina; 3) combining said treated alumina with triethylaluminum andbis(n-butylcyclopentadienyl) zirconium dichloride.
 21. A processaccording to claim 1, wherein said catalyst composition is produced by aprocess consisting essentially of contacting said organometal compound,said treated solid oxide compound, and said organoaluminum compound. 22.A process according to claim 1, wherein said at least one organometalcompound is selected from: bis(cyclopentadienyl) hafnium dichloride;bis(cyclopentadienyl) zirconium dichloride; [ethyl(indenyl)₂] hafniumdichloride; [ethyl(indenyl)₂] zirconium dichloride;[ethyl(tetrahydroindenyl)₂] hafnium dichloride;[ethyl(tetrahydroindenyl)₂] zirconium dichloride;bis(n-butylcyclopentadienyl) hafnium dichloride;bis(n-butylcyclopentadienyl) zirconium dichloride;((dimethyl)(diindenyl)silane) zirconium dichloride;((dimethyl)(diindenyl)silane) hafnium dichloride;((dimethyl)(ditetrahydroindenyl)silane) zirconium dichloride;((dimethyl)(di(2-methyl indenyl)) silane) zirconium dichloride;bis(fluorenyl) zirconium dichloride; or mixtures thereof.
 23. A processaccording to claim 1, wherein said at least one organoaluminum compoundis selected from trimethylaluminum, triethylaluminum, tripropylaluminum,diethylaluminum ethoxide, tributylaluminum, triisobutylaluminum hydride,triisobutylaluminum, diethylaluminum chloride, or mixtures thereof. 24.A process according to claim 1, wherein said at least one solid oxidecompound is selected from Al₂O₃, B₂O₃, BeO, Bi₂O₃, CdO, Co₃O₄, Cr₂O₃,CuO, Fe₂O₃, Ga₂O₃, La₂O₃, Mn₂O₃, MoO₃, NiO, P₂O₅, Sb₂O₅, SiO₂, SnO₂,SrO, ThO₂, TiO₂, V₂O₅, WO₃, Y₂O₃, ZnO, ZrO₂, mixed oxides thereof, ormixtures thereof.
 25. A process according to claim 24, wherein said atleast one solid oxide compound is selected from silica-alumina orsilica-zirconia.
 26. A process according to claim 14, wherein said atleast one solid oxide compound is selected from silica-alumina orsilica-zirconia.